CN115893844A - Preparation method of ultra-smooth ceramic glaze - Google Patents
Preparation method of ultra-smooth ceramic glaze Download PDFInfo
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- CN115893844A CN115893844A CN202211466881.7A CN202211466881A CN115893844A CN 115893844 A CN115893844 A CN 115893844A CN 202211466881 A CN202211466881 A CN 202211466881A CN 115893844 A CN115893844 A CN 115893844A
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- glaze
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- overglaze
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- 239000000919 ceramic Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 239000010453 quartz Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 235000019738 Limestone Nutrition 0.000 claims abstract description 8
- 239000006028 limestone Substances 0.000 claims abstract description 8
- 239000000454 talc Substances 0.000 claims abstract description 8
- 229910052623 talc Inorganic materials 0.000 claims abstract description 8
- 239000010456 wollastonite Substances 0.000 claims abstract description 8
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 8
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000010436 fluorite Substances 0.000 claims abstract description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910052656 albite Inorganic materials 0.000 claims abstract description 4
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010433 feldspar Substances 0.000 claims abstract description 4
- 229940072033 potash Drugs 0.000 claims abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims abstract description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims 2
- 241000894006 Bacteria Species 0.000 abstract description 4
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002103 nanocoating Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The invention discloses a preparation method of an ultra-smooth ceramic glaze, which consists of a ground glaze and a surface glaze; the ground glaze comprises the following raw materials of 20-24 wt% of quartz, 8-10 wt% of potassium feldspar, 18-20 wt% of albite, 5-6 wt% of kaolin, 1-2 wt% of zinc oxide, 1-2 wt% of talc, 7-9 wt% of wollastonite, 7-9 wt% of high-temperature frit, 11-14 wt% of limestone, 1-2 wt% of aluminum oxide and 8-12 wt% of zirconium silicate; the overglaze comprises the raw materials of 24-30 wt% of quartz, 26-32 wt% of potash feldspar, 6-10 wt% of kaolin, 1-3 wt% of zinc oxide, 3-6 wt% of talc, 4-8 wt% of wollastonite, 8-12 wt% of limestone, 2-4 wt% of fluorite, 10-18 wt% of high-temperature frit and 2-4 wt% of additives. The invention adopts a double-layer glazing method and simultaneously optimizesThe formula is formed by introducing SrCO into overglaze 3 、RbCl、Y 2 O 3 The additive reduces the roughness of the glaze, makes the glaze smoother, more compact and smoother, and achieves the purposes of effectively preventing the adhesion of dirt and bacteria and having good anti-fouling effect.
Description
Technical Field
The invention relates to the technical field of ceramic glaze, in particular to a preparation method of an ultra-smooth ceramic glaze.
Background
At present, the yield of the building sanitary ceramics in China is the first in the world and is also the largest building sanitary ceramics consumption market in the world, but the overall economic benefit is not high. The main difference from foreign products is that the glaze surface has the defects of tiny pinholes, concave-convex and the like, and dirt, bacteria and the like are easy to deposit at the defect part in the using process, so that the attractiveness of the ceramic product is influenced, the cleaning difficulty is increased, and the detergent used in the cleaning causes environmental pollution; meanwhile, the pollutants can provide nutrients for microorganisms such as bacteria on the surface of the glaze layer, so that mass propagation is caused, and the health of people is influenced. With the improvement of living standard of people, technical innovation is very important to meet high requirements of consumers on the appearance quality and sanitation of ceramics.
At present, the prior art has measures for improving the pollution resistance of ceramics: (1) Coating an antifouling coating such as a hydrophobic coating on the surface of the glaze layer; (2) Introducing a nano antibacterial material into the glaze so as to improve the antibacterial property of the glaze; (3) The glaze smoothness is improved by adopting a proper glaze formula and a firing process. Most of the existing self-cleaning glazes adopt a method of adding an antibacterial agent and an organic nano coating technology in the glaze. When the coating is adopted, the coating is damaged due to abrasion in the using process, the service life is usually 3-5 years, and the production cost of the product is relatively high. The ceramic antibacterial glaze has good antibacterial effect under the excitation of ultraviolet light, but the antibacterial effect is greatly reduced when the ceramic antibacterial glaze is used in a dark environment or a humid environment. Both the two technologies can greatly increase the production cost, the service life of the nano coating of the glaze surface is short, and a plurality of problems of glaze shrinkage, glaze breakage and the like can occur in the actual production by adding the antibacterial agent, and the precision requirement on the temperature in the firing process is high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an ultra-smooth ceramic glaze, which adopts a method of applying a cover glaze on a ground glazeThe double-layer glazing method simultaneously optimizes the formula composition and introduces SrCO into the overglaze 3 、RbCl、Y 2 O 3 The formed additive is used for reducing the roughness of the glaze surface, so that the glaze surface is smoother, more compact and smoother, and the aims of effectively preventing dirt and bacteria from adhering and having good anti-fouling effect are fulfilled.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of an ultra-smooth ceramic glaze, wherein the ceramic glaze consists of a ground glaze and a surface glaze; the ground glaze comprises the following raw materials of 20-24 wt% of quartz, 8-10 wt% of potassium feldspar, 18-20 wt% of albite, 5-6 wt% of kaolin, 1-2 wt% of zinc oxide, 1-2 wt% of talc, 7-9 wt% of wollastonite, 7-9 wt% of high-temperature frit, 11-14 wt% of limestone, 1-2 wt% of aluminum oxide and 8-12 wt% of zirconium silicate; the overglaze comprises the raw materials of 24-30 wt% of quartz, 26-32 wt% of potash feldspar, 6-10 wt% of kaolin, 1-3 wt% of zinc oxide, 3-6 wt% of talc, 4-8 wt% of wollastonite, 8-12 wt% of limestone, 2-4 wt% of fluorite, 10-18 wt% of high-temperature frit and 2-4 wt% of an additive, wherein the additive is formed by SrCO 3 、RbCl、Y 2 O 3 Composition of SrCO according to mass ratio 3 ∶RbCl∶Y 2 O 3 = 1-2: 0.5-1; the preparation method comprises the following steps:
(1) Weighing the raw material composition of the ground glaze and the raw material composition of the surface glaze respectively, mixing, performing wet ball milling, and sieving to obtain ground glaze slip with the median particle size of 200-250 meshes and surface glaze slip with the median particle size of 200-250 meshes;
(2) Putting the ceramic green body into the ground glaze slip, and applying ground glaze on the surface of the ceramic green body in a glaze dipping mode; drying the ceramic green body with the ground coat, then putting the ceramic green body into the overglaze slip, and applying overglaze on the surface of the ground coat in a glaze dipping mode; then drying and putting into a kiln for one-time firing, wherein the sintering system is to heat the mixture from room temperature to 1180-1250 ℃ at the heating rate of 5-15 ℃/min, the heat preservation time is 30-90 min, and the mixture is naturally cooled to room temperature along with the furnace, so that the ultra-smooth ceramic glaze is obtained.
Furthermore, the median particle sizes of quartz, zinc oxide, alumina, fluorite and the additive in the raw materials are all 60-80 meshes, and the median particle sizes of the other raw materials are all 60-120 meshes.
In the scheme, the specific gravity of the bottom glaze slip in the step (1) is 1.70-1.75 kg/L, and the specific gravity of the surface glaze slip is 1.62-1.68 kg/L. In the step (2), the glaze dipping time of the mid-sole glaze is 2-4 s, and the glaze dipping time of the overglaze is 1-3 s. The surface roughness Ra of the ultra-smooth ceramic glaze is 0.013-0.028 mu m.
The invention has the following beneficial effects:
(1) The invention applies a layer of RbCl and SrCO introduced on the glaze surface of the ground coat by optimizing the formula composition and adopting a two-step glazing method 3 、Y 2 O 3 Overglaze of additive, rbCl, srCO in additive 3 With K in overglaze raw material 2 The fluxing components such as O, caO, mgO and the like can form multi-eutectic compounds in the high-temperature firing process, the initial melting temperature of the overglaze is effectively reduced, the viscosity of the high-temperature liquid phase of the overglaze is favorably reduced, the defects of pinholes, bubbles and the like in the overglaze are reduced, the smoothness and the flatness of the whole overglaze are favorably improved, and the appearance and the use quality of ceramic products are improved.
(2) RbCl and SrCO in overglaze additive 3 、Y 2 O 3 Contain high atomic number's univalent, divalent and trivalent cation respectively, synergism under the mixed alkali effect, under the circumstances that guarantees that the glaze has good high temperature mobility, can effectively increase glaze melting temperature range, let the gaseous component of decomposable out in the glaze have abundant time with gaseous discharge, reduce the roughness of glaze, be favorable to the promotion of glaze smooth effect, promote glaze quality, make the filth be difficult to the adhesion on the glaze, easily wash, possess better anti-soil effect.
The present invention will be described in further detail with reference to examples.
Detailed Description
The embodiment of the invention provides a preparation method of an ultra-smooth ceramic glaze, wherein the ceramic glaze consists of a ground glaze and a surface glaze; the raw material composition of the ground coat is 24wt% of quartz, 9wt% of potassium feldspar, 19wt% of albite and kaolin6wt% of soil, 2wt% of zinc oxide, 1wt% of talc, 8wt% of wollastonite, 8wt% of high-temperature clinker, 12wt% of limestone, 1wt% of alumina and 10wt% of zirconium silicate; the overglaze is prepared from quartz 24-30 wt%, potash feldspar 26-32 wt%, kaolin 6-10 wt%, zinc oxide 1-3 wt%, talc 3-6 wt%, wollastonite 4-8 wt%, limestone 8-12 wt%, fluorite 2-4 wt%, high-temperature frit 10-18 wt%, and additive 2-4 wt%, wherein the additive is SrCO 3 、RbCl、Y 2 O 3 Composition of SrCO according to mass ratio 3 ∶RbCl∶Y 2 O 3 = 1-2: 0.5-1; the raw material composition and additive composition of the overglaze of each example are shown in table 1; in the raw materials used in the embodiment of the invention, quartz, zinc oxide, alumina, fluorite and additives are all industrial pure, and the median particle size is 60-80 meshes; the chemical compositions of the rest raw materials are shown in table 2, and the median particle diameters are all 60-120 meshes;
the preparation method comprises the following steps:
(1) Weighing the raw material composition of the ground glaze and the raw material composition of the surface glaze respectively, mixing, performing wet ball milling (material: ball: water = 1: 2: 0.5) for 180min, and sieving to obtain ground glaze slip with the median particle size of 200-250 meshes and the specific gravity of 1.72kg/L and surface glaze slip with the median particle size of 200-250 meshes and the specific gravity of 1.65 kg/L;
(2) Putting the ceramic green body into the ground glaze slip, applying ground glaze on the surface of the ceramic green body in a glaze dipping mode, wherein the ground glaze dipping time is 2-4 s; putting the ceramic green body with the ground glaze into a constant-temperature drying box at 100 ℃ for drying until the water content is less than 1%, then putting the ceramic green body into the overglaze glaze slip, and applying overglaze on the surface of the ground glaze in a glaze dipping mode for 1-3 s; then drying and putting into a kiln for one-time firing, wherein the sintering system is to heat the mixture from room temperature to 1180-1250 ℃ at the heating rate of 5-15 ℃/min, the heat preservation time is 30-90 min, and the mixture is naturally cooled to room temperature along with the furnace, so that the ultra-smooth ceramic glaze is obtained. The process parameters for each example are shown in table 3.
TABLE 1 composition of the raw materials and additive for overglaze of each example of the present invention
* Is in proportion by mass
TABLE 2 chemical composition (wt%) of raw materials used in examples of the present invention
Table 3 process parameters of the preparation method of each example of the present invention
In the case of the fifth example described above without the addition of additives (i.e., without the addition of SrCO) 3 、RbCl、Y 2 O 3 ) Is a comparative example. The performance test indexes of the ultra-smooth ceramic glaze prepared in the embodiment of the invention and the comparative example are shown in Table 4:
table 4 test performance indexes of inventive examples and comparative examples
As can be seen by the performance tests of table 4: the glaze roughness of the ultra-smooth glaze ceramic body in the embodiment of the invention is optimally 0.013 mu m; the roughness of the glaze surface of example five is reduced by 77.59% compared with that of the comparative example.
Claims (5)
1. A preparation method of an ultra-smooth ceramic glaze is characterized by comprising the following steps: the ceramic glaze consists of a ground glaze and a surface glaze; the ground glaze comprises the following raw materials of 20-24 wt% of quartz, 8-10 wt% of potassium feldspar, 18-20 wt% of albite, 5-6 wt% of kaolin, 1-2 wt% of zinc oxide, 1-2 wt% of talc, 7-9 wt% of wollastonite, 7-9 wt% of high-temperature frit, 11-14 wt% of limestone, 1-2 wt% of alumina and 8-12 wt% of zirconium silicate; the overglaze is prepared from quartz 24-30 wt%, potash feldspar 26-32 wt%6 to 10 weight percent of kaolin, 1 to 3 weight percent of zinc oxide, 3 to 6 weight percent of talcum, 4 to 8 weight percent of wollastonite, 8 to 12 weight percent of limestone, 2 to 4 weight percent of fluorite, 10 to 18 weight percent of high-temperature frit and 2 to 4 weight percent of additive, wherein the additive is formed by SrCO 3 、RbCl、Y 2 O 3 Composition of SrCO according to mass ratio 3 ∶RbCl∶Y 2 O 3 = 1-2: 0.5-1; the preparation method comprises the following steps:
(1) Weighing the raw material composition of the ground glaze and the raw material composition of the surface glaze respectively, mixing, performing wet ball milling, and sieving to obtain ground glaze slip with the median particle size of 200-250 meshes and surface glaze slip with the median particle size of 200-250 meshes;
(2) Putting the ceramic green body into the ground glaze slip, and applying ground glaze on the surface of the ceramic green body in a glaze dipping mode; drying the ceramic green body with the ground coat, then putting the ceramic green body into the overglaze slip, and applying overglaze on the surface of the ground coat in a glaze dipping mode; then drying and putting into a kiln for one-time firing, wherein the sintering system is to heat the mixture from room temperature to 1180-1250 ℃ at the heating rate of 5-15 ℃/min, the heat preservation time is 30-90 min, and the mixture is naturally cooled to room temperature along with the furnace, so that the ultra-smooth ceramic glaze is obtained.
2. The method for preparing an ultra-smooth ceramic glaze according to claim 1, wherein: the median particle sizes of quartz, zinc oxide, alumina, fluorite and the additive in the raw materials are all 60-80 meshes, and the median particle sizes of the other raw materials are all 60-120 meshes.
3. The method for preparing an ultra-smooth ceramic glaze according to claim 1, wherein: the specific gravity of the middle-layer glaze slip in the step (1) is 1.70-1.75 kg/L, and the specific gravity of the surface glaze slip is 1.62-1.68 kg/L.
4. The method for preparing an ultra-smooth ceramic glaze according to claim 1, wherein: in the step (2), the glaze dipping time of the mid-sole glaze is 2-4 s, and the glaze dipping time of the overglaze is 1-3 s.
5. The method for preparing an ultra-smooth ceramic glaze according to claim 1, wherein: the surface roughness Ra of the ultra-smooth ceramic glaze is 0.013-0.028 mu m.
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|---|---|---|---|
| CN202211466881.7A CN115893844B (en) | 2022-11-22 | 2022-11-22 | Preparation method of ultra-smooth ceramic glaze |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211466881.7A CN115893844B (en) | 2022-11-22 | 2022-11-22 | Preparation method of ultra-smooth ceramic glaze |
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| CN115893844A true CN115893844A (en) | 2023-04-04 |
| CN115893844B CN115893844B (en) | 2024-01-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302581A (en) * | 1999-04-13 | 2000-10-31 | Toto Ltd | Antifouling glazed product |
| JP2003300771A (en) * | 2002-04-02 | 2003-10-21 | Toto Ltd | Sanitary earthenware |
| CN101875567A (en) * | 2010-06-04 | 2010-11-03 | 深圳市永丰源实业有限公司 | Exquisite glaze, exquisite ceramic and preparation process of exquisite ceramic |
| CN109942190A (en) * | 2019-03-14 | 2019-06-28 | 江西和美陶瓷有限公司 | Anti-skidding matt ceramic brick |
| CN110627359A (en) * | 2019-11-04 | 2019-12-31 | 江西飞宇新能源科技有限公司 | Frit for glaze and preparation method thereof |
| CN111253071A (en) * | 2020-05-06 | 2020-06-09 | 佛山东鹏洁具股份有限公司 | High-stain-resistance FFC glaze, FFC sanitary ceramic and preparation method thereof |
| CN112028487A (en) * | 2020-09-25 | 2020-12-04 | 广东四通集团股份有限公司 | Preparation method of wear-resistant glaze daily porcelain glaze |
| CN113264784A (en) * | 2021-07-20 | 2021-08-17 | 佛山市东鹏陶瓷发展有限公司 | Toughened prestressed building ceramic and preparation method thereof |
-
2022
- 2022-11-22 CN CN202211466881.7A patent/CN115893844B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302581A (en) * | 1999-04-13 | 2000-10-31 | Toto Ltd | Antifouling glazed product |
| JP2003300771A (en) * | 2002-04-02 | 2003-10-21 | Toto Ltd | Sanitary earthenware |
| CN101875567A (en) * | 2010-06-04 | 2010-11-03 | 深圳市永丰源实业有限公司 | Exquisite glaze, exquisite ceramic and preparation process of exquisite ceramic |
| CN109942190A (en) * | 2019-03-14 | 2019-06-28 | 江西和美陶瓷有限公司 | Anti-skidding matt ceramic brick |
| CN110627359A (en) * | 2019-11-04 | 2019-12-31 | 江西飞宇新能源科技有限公司 | Frit for glaze and preparation method thereof |
| CN111253071A (en) * | 2020-05-06 | 2020-06-09 | 佛山东鹏洁具股份有限公司 | High-stain-resistance FFC glaze, FFC sanitary ceramic and preparation method thereof |
| CN112028487A (en) * | 2020-09-25 | 2020-12-04 | 广东四通集团股份有限公司 | Preparation method of wear-resistant glaze daily porcelain glaze |
| CN113264784A (en) * | 2021-07-20 | 2021-08-17 | 佛山市东鹏陶瓷发展有限公司 | Toughened prestressed building ceramic and preparation method thereof |
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| CN115893844B (en) | 2024-01-30 |
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